Sensitized photographic emulsion



July 8, 1947. KNOTT 2,423,710

SENSITIZED PHOTOGRAPHIC EMULSION Filed April 12, 1945 3 Sheets-Sheet: 1

I I- d/ 2 2'- lbdide FIG. I.

320 36 4o 44 48 52 56 so 6 10M,

2,2 lbdide and FIG. 2.

fad/Henna FIG.3.

fad/He and scmicarbazone 2-' Ibd/b'emd FIG. 5.

22 l'odideand FIG 6 EDWARD B.KNOTT INVEIYTOR p0 A I 7ORNEYS y 1947- E. B. KNOTT 2,423,710

SENSITIZED PHOTOGRAPHIC EMULSIQN Filed April 12, 1945 3 Sheets-Sheet 2 2,2" Ind/He and inocinnamic FIG. 7.

' -2 iodide FIG. 8.

' fad/He and jemic'arbazone FIG. 9.

FIG. I0.

320 as I- efh -3 ia- 2'- Iodide FIG I I 32a 36 I '40 44 4a 52 56 60 Mp. llbdide and mica/M2 11 FIG. I.

EDWARD B. KNOTT I INVENTOR I 2' -fM/M I EM J- AHORNEYS y 1947- E. B. KNOTT 2,423,710 SENS'ITIZED PHOTOGRAPHIC EMULSION I Filed April 12, 1945 5 Sheets-Shet 3 I'M/Henna Je/n/barbazone FIG. I3.

ma z' v .920 mom 4 iodide FIG. 15.

'lbd/He and Jemicarbazone FIG.I6.

/'odide and FIG.I7

EDWARD B. KNOTT INVbINTOR Patented July 8, 1947 U NI TIED STAT E S 11C E g 2,423,710 I 'SENSITIZED PHOTOGRAPHIb EMULSION Edward B. Knott, Wealdstonefilflnglan'd,"assignor to Eastman Kodak Company-Rochesterf-NI Y-., a corporation of New Jersey Application April 12, 1945,;Seri21 -NQ .57,17

In Great Britain MayT18,.'19'44 This invention relates to sensitized photo'- graphi'c emulsions and more particularlyto spec 'trally (optically) sensitized emulsions.

It is known that the distribution of spectral sensitivity of certain spectrally sensitized (i. e.

dye-sensitized) emulsions can be altered and an increase in sensitivity obtained insome spectral region, by incorporating certain additional sensitizing dyes in the spectrally sensitized emulsions. S'ee United States Patents 2,158,882, dated May '16, 1939, and 2,159,565, dated May 23, 1939.) The effect thus obtained has'come to be known as supersensitization. Supersensitizati'on of certain spectrally sensitized emulsions can also be eflected by incorporatingcertain substantially colorless heterocyclic bases, viz. those containing an amino group, in'the spectrally sensitized'emulsions. (See United States Patent 2,177,635, dated October 31, 1939.) Supersensitization differs from hypersensitization whichinvolves bathing of finished plates or films, an operation which normally reduces thepAg and increases the pH of the emulsions with. eonsequentdecreased stability. 7 I :have now found a new method for super- .sensitizinglspectrally sensitized emulsions, which not. only. does not reduce the stability of the emulsions, .butis valuable as a means of securing spectrally. sensitized emulsions of increased speed. ..It is, accordingly, an object of my invention to provide new supersensi-tized photographic emul-.

sions. A further object is to provide aprocess for preparing such emulsions. Still other objects will become apparent hereinafter.

In accordance with myinvention, a photographic silver halide emulsion :spectrally sensitized with ,3, 2" cyanine dye or an oxacanbocyamne dyeissupersensitized by incorporating-in the 'emulsion'at-i least one organic compound selected 'froml't'hose represented by the following general formula:

N (CH' 'CH) a1=o=z f/ R1 wherein R1- and R2 each represents analliyl group, n represents a positive integer ofwfrom 1 to 6, R represents a member selected from the group consisting of hydrogen, an alkyl group, an aralkyl group, an laryl'group and agroupof the following general formula:

"wlierein R1 and R2 and n have'the values given above, '2 represents a member selected-from the group consistin'gof a hydraz ono group','an alkylhydrazonc "group, "a; di'alkylhy'drazono group, an aralkylhydr'aizo'noigroup, a "diaralkylhydra'zono group,"anarylhydrazonogroup, a diarylhydrazono group, a; "hydroziminogroup; a carbamylhydrazonc group, "a thiocarbainylhydrazono group and a guanylhydrazono group when n represents a positive-integerof from 1 to 6, and when rep"- resents 'apositiv'einteger'of "from 2 to 6, 'Z represents an oxygen atom in-addit'ion to'th'egr'oups recited above 'for Z. Y

- The compounds whioh Iincorporate in the spectiially sensitized emulsion, include hydraz'one's, se'micarbazones, thio'semicarba'zones, oximes' and aniinoguanides, as well as the corresponding car-- ibonyl compounds 'in some cas'es.

vTliypi'cal names of these compounds include: pl ia lkylaminocinnamic aldehydes p D'ialkylla'ininob'enzal ac''tones p pialkylaminobenzal 'acetophenon'es 'p- Dialkylaminocinnainal aoetophenons v I p-Dialkyl'aminocinnamic aldehyde phe'nyl hydrazones peljialkylaminocinnanfic amehya hydrazonjes p-Dialkyla inocinnamic aldehyde semicarbazones v p-Dialkyla'minocinnamic aldehyde 'gu'anides p-Dialkylbenzal acetone semicarbiazones .Bisi (p dialkylaminobenzal aoetones') p-Dialkylaminocinna'micaldehyde oximes -'The sensitizing dyes which I employ in practic= ing my invention "fall'within' the class of 2"'-'cy'a"- nine dyes and the class of oxac arbocyanine 'd'yes.

supersen'si tizing"effectsobtaine'd with the 2'- cyanine dyes (especially the 1;1"-dialkyl-2,2'- cyanine' salts) are much more marked than the effects which can be obtained with the o-xacarbocyam'ne dyes. By the term -2"-'cyanine dye, I mean ia'monomethinecyan-ine dye containing a quinoline nucleus linked through its vzor 2 posi tion to another heterocyclic nucleus-through the aor 2-position of the second heterocyclic nucleuso By the term oxa'c'arbocyanine dyes, I mean a carbocyanine dyecontaimng two benzoxazole nuclei. Among the 2'-c'ya'nin'e dyes and oxaoar bocyanine dyes which I em by in practicing my invention are the following:

1, dialkyl-2,2'-cyanine salts; e. g. 1,'l'-diethyl- ,2'-cyanine halides, such as the iodide. 3,1-dialkylbenzothia-2"-cyanine salts, e. g. 3-

methyl 1- ethylbenzothia-2-cyanine halides,

such 'as th bromide.

. art.

3,1-dialkylthia-2-cyanine salts, e. g. 3-methy1- -ethylthia-2'-cyanine halides, such as the iodide.

3,1-dialkylselena-2'-cyanine salts, e. g. 3,1 -diethylse1ena-2'-cyanine halides, such as the iodide.

3,3'-dialkyloxacarbocyanine salts, e. g. 3,3'-diethyl or 3,3,9-triethyloxacarbocyanine halides, such as the iodide.

The sensitizing dyes can be employed in any desired concentration. Ordinarily from to 30 mg. of dye per liter of emulsion (containing about 0.25 gram-moles of silver halide) will suffice to produce the optimum sensitizing efiect. methods of incorporating sensitizing dyes in emulsions are well known to those skilled in the Ordinarily, it is preferable to dissolve the dye in a water-miscible solvent, such as methanol, and incorporating the methyl alcoholic solution in the emulsion. Ethyl alcohol or acetone may be employed instead of methanol. One or 7 more sensitizing dyes can be employed.

Ordinarily, the supersensitizing compound is incorporated in the emulsion which already contains the sensitizing dye or dyes. However, the supersensitizing compound can be incorporated in the emulsion before the sensitizing dye or dyes, or the supersensitizing compound and the sensitizing dye or dyes can be incorporated in the emulsion simultaneously. Usually the super-sensitizing compounds are incorporated in the emulsion in a concentration equal to from about 10 to about 300 mg. for that quantity of silver halide emulsion equivalent to 200 grams of silver nitrate. The optimum concentration for process-type emulsions is usually of the order of 100 mg. for that quantity of silver halide emulsion equivalent to 200 grams of silver nitrate. The supersensitizing compounds are preferably but not necessarily dissolved in a watermiscible solvent, such as methanol before incorporation in the emulsion. One or more of the supersensitizing compounds can be employed and the supersensitizing compounds as well as the sensitizing dyes can be added to the emulsion during any suitable stage of its preparation. Usually both the supersensitizing compounds and the supersensitizing dyes are advantaegously added. to the washed, finished emulsions,

To determinev the optimum concentration of any' of the supersensitizing compounds, a batch of emulsion is first sensitized with the sensitizing dye in such quantity as to give optimum speed. Another batch of the same emulsion is similarly sensitized and several portions of this batch of emulsion are treated with various concentrations of the supersensitizing compound. Each of the portions of emulsion is then coated and exposed and processed as usual. The increase in the minus blue speed of the emulsion at optimum supersensitizer concentration is taken as a measure of the supersensitizing action of the compound. Wedge spectrograms also indicate this measure.

The accompanying drawings show diagrammatically the speotrograms of emulsions containing sensitizing dyes with and without the supersensitizing compounds of the present invention. a

The compositions of the emulsions are given in the following examples which are numbered to correspond to the figure numbers in the drawings.

- Erample 1 A gelatino-silver-bromiodide developing-out in a concentration of 100 mg.'per that quantity The' of emulsion equivalent to 200 grams of silver nitrate. The sensitizing effect of this quantity of dye is depicted in Fig. 1 of the accompanying drawing.

Example 2 hyde semicarbazone in a concentration of 100 mg.

per that quantity of emulsion equivalent to 200 grams of silver nitrate. The resulting emulsion showed an increase ingreen sensitivity of 300 per cent over the green sensitivity of the emulsion of Example 1. This increase in sensitivity is apparent from Fig. 2 of the accompanying drawing which depicts the sensitivity'of the emulsion of the instant example;

Example 3 To a gelatino-silver-bromiodide developing-out V emulsion, dye-sensitized as in-Example l, was

added p-dimethylaminocinnamic aldehyde in a concentration of mg. per that quantity of emulsion equivalent to 200 grams of silver nitrate. The resulting emulsion showed an increase in green sensitivity of '700 per cent over the green sensitivity of the emulsion of Example 1. This increase in green sensitivity is apparent from Fig. 3 which depictsthe sensitivity of the emulsion of the instant example. I

Example 4 Example 5 To a gelatino-silver-bromide developing-out emulsion, dye-sensitized as in Example 1, was

added p-dimethylaminocinnamic aldehyde ami-- noguanide in a concentration of 100 mg. per that quantity of emulsion equivalent to 200 grams of silver nitrate. The resulting emulsion showed an increase in green sensitivity of700 per cent over the green sensitivity of the emulsion of Example 1. This increase in green sensitivity is apparent from Fig. 5 of the accompanyin drawing which depicts the sensitivity of the instant emulsion.

Example To a gelatino-silver-bromiodide developing-out emulsion, dye-sensitized a in Example 1, .was added p-dimethylaminocinnamic aldehyde phenylhydrazone in a concentration of 100 mg. per that quantity of emulsion equivalent to 200 grams of silver nitrate. Theresulting emulsion showed an ncr ase in reen sensitivit rsoo per cent overthe' green sensitivity. ot the emulsion of: Example 1'. 'I-hi'sincrease ingreen sensitivity is apparent. iromFigz': fi ofothe accompanying drawing which: depicts the sensitivity-of the instant emul= sion. I

Example 7 To a.gelatinoesilver-bromiodide developin -out emulsion, [dye-sensitized as. in. Example 1,, was added pedim'ethylaminocinnamic .aldehyde.v hydrazone aconcent'ration of 100.,mg.,per that quantityiofemulsionequivalent to 200' gramsv of silver nitrate." The resulting emulsionshowed, an increase in. green sensitivity of 300. oer cent. over the green sensitivity of the emulsion of Example. 1. This increase in green sensitivity is apparent from-Fig; '7 ofthe accompanying drawing which depicts thesensitivityofthe instant emulsion.

Using the :below-listed compounds instead of p-c l-imethylaminocinnamic-v aldehyde hydrazone, at :the. same concentration, various increasesin the. minus blu speed of the emulsion of Example l -were obtained as indicated:

r Minus blue speed increase, per cent p-Dimethyl'aminobenzalacetophenone p-Dimethylaminocinnamalacetophenone p-Dimethylaminobenzalacetone peDimethylaminobenzalacetone semicarb-azone 700 p-Dimethylaminocinnamalacetone 700 Bis-(p dimethylaminohenzal)- acetone 5.00

Example 8 A gelatino-silver bromiodide developingeout emulsion was sensitized with 1',3-diethyl-6- methylr-4,5-benzth-iae2-'--cyanine iodide having'the formula:

in a concentration equal to 100 mg. of the cyanine iodide perthat quantity of emulsion equivalent to 200; grams of. silver nitrate. The, sensitizing oftheaccompanying drawing.

.. Example} 9 To a gelatino-silver-bromiodide developing-out emulsion, dye-sensitized a in Example 8, was added p-dimethylaminocinnamic aldehyde amino-guanide in a concentrationof 100mg. per that quantity of emulsion equivalent to 200 grams of silver nitrate. 'The resultingemulsionshowed an increaseingreensensitivityof- .30 per cent over the green-sensitivity of the emulsion of Example 1.

effect of this quantity of dye is depicted in Fig; 8

6 This increase in green sensitivity is: apparent fromli'ig; '10. of the accompanying drawing which depicts the sensitivityof the instant emulsion.

. Example 11 A gelatino-tsilver bromiodide: developing-out emulsion waswsensitized; with 1-ethyl-3-methylthid-2'-cyanine.iodide having the formula:

in a concentration equal to v mg. of the cyanine iodideper'that quantity of emulsion equivalentto 200., grams offsilver nitrate. 'The. sensitizing ,effect of this. quantity. of. dye i ,depictedin Fig. 11 of.theaccompanyin drawing.

' Example 1 2 To a gelatino silverebromiodide developing-out emulsion,,dye-sensitized as in Example 11, was added. p-dimethylaminocinnamic semicarbazone ina concentration of: 100' mg. per'that, quantity of emulsion equivalent to.200 mg. of'silver nitrate. The resu1ting emulsion showed an increasejin green. sensitivity 01150 per cent over'the green sensitivity, of the. emulsion of Example 11. This increasein green sensitivity is apparent fromTig. 12 of the accompanying-drawing which depicts the sensitivity ofthe instant emulsion.

' Example 13 To a gelatinoesilver-bromiodide developing-out emulsion, dye-sensitized as in-Example 11, was added p-dimethylaminocinnamic aldehyde aminoguanide; in a concentration of 100 mg. per that quantityof emulsion equivalent to 200 mg. of silvernitrate. .Theresultin emulsion-showed an increase in green: sensitivity of 100 per cent over the; green sensitivity of the, emulsionof Example 11. This increase in green sensitivitycan be seen from Big. ,13 of :the accompanying drawing which deplctsthe sensitivityof the; instant emulsion.

, -Eaumple, 15

A gelatino-silver-bromiodide developing-out emulsion: was sensitized with 3, 3- diethyloxacarbocyanine iodide having the formula in aconcentr'ation equal to 100 mg. ofthe carbocyanineiodide per-:that quantity of emulsion equivalent to-200 grams .ofi-silverinitrate. 1 The 7 sensitizing effect of this quantity of dyeis depicted in Fig. 15 of the accompanying. drawing.

Example 16 Example 17 To a gelatino-silver-bromiodide developing-out emulsion, dye-sensitized as in Example 15, was added p-dimethylaminocinnamic aldehyde aminoguanide in a concentration of 100 mg. per that quantity of emulsion equivalent to 200 mg. of silver nitrate. The resulting emulsion showed an increase in green sensitivity of 30 per cent over the green sensitivity of emulsion of Example 15. This increase in green sensitivity is apparent from Fig. 16 of the accompanying drawing which depicts the sensitivity of the instant emulsion.

In a manner similar to that illustrated in the foregoing examples other 2'-cyanine dyes and oxacarbocyanine dyes can be supersensitized with one or more of the compounds represented by the foregoing general formula.

My invention i primarily directed to the customarily employed gelatino-silver-halide developing-out emulsion, such as gelatino-silverchloride, gelatino-silver-chlorobromide, gelatino-silver-bromide, and gelatino silver bromiodide emulsions.

Emulsions prepared in accordance with my inventioncan be coated in the usual manner upon anydesired support, such as cellulose nitrate film,

cellulose acetate film, polyvinyl acetal resin film,

metal support, glass support or paper support. 7

The supersensitizing compounds which I employ in practicing my invention are known or can be readily prepared. The preparationsof several compounds are illustrated in the following examples. I

Example 18. p-Dimethylammobenzalacetopher 7.45 g. of 'p-dimethylaminobenzaldehyde and 6 g. of acetophenone were dissolved in 40 cc. of ethyl alcohol. To this solution were added 5 cc.

of a 10 per cent (by weight) aqueous solution of sodium hydroxide. The resulting mixture was allowed to stand at 25C. for 4 hours. Then a little water was added until the mixture became cloudy. After a while, white large glistening plates separated out. These were recrystallized from aqueous ethyl alcohol and obtained as yellow-needles melting at 110 to 112 C. Similarly other p-dialkylaminobenzalacetophenones can be prepared.

Errample 19. -p Dimethylaminocinnamalacetophenone added to the solution. Upon cooling the resulting mixture, glistening red plates separated out.

After 12 hours standing, the redplates were'filtered off and recrystallized from ethyl alcohol. Glistening' fiat red needles were obtained, melting at 154 to 155C. 7 Similarly other p-dialkylaminocinnamalacetophenones can be prepared.-

Example 20.--p-Dimethylaminob enzalacetone 7 .45 g. of p-dimethylamino'benzaldehyde and 2.9 g. of acetone were dissolved in,50 cc. of ethyl alcohol and 5 cc. of 10 per cent (by weight) of aqueous sodium hydroxide were added. The liquor set after several hours. The material was recrystallized from ethyl alcohol and obtained as yellow needles, melting at 120 to 123 C. Similarly other p-dialkylaminobenzalacetones can be prepared.

Example 21 .-p-Dimethylcinnamalacetone Example 22.Bz' s-(1 -dimethylaminobenzalacetone) i 7.45 g. of p-dimethylaminobenzaldehyde, 1.45 g. of acetone and 50 cc. of ethyl alcohol were heated to give a solution. 10 cc. of'10 per cent (by weight) of aqueous sodium hydroxide were added to the solution and the resulting mixture was allowed to stand'for 48 hours. An orange powder separated which was recrystallized from ethyl alcohol, forming'glistening orange plates melting at to 196 C. Similarly other bis- (pdialkylaminobenzalacetones) can be prepared, as can bis-(p-dialkylaminocinnamal acetones).

The hydrazones. semicarbazones, oximes and aminoguanides of the carbonylic compounds can be prepared by refluxing the carbonylic compounds with a hydrazine salt, a semi-carbazide salt, a'hydroxylamine salt or an aminoguanidine salt, in ethyl alcohol, in the presence of sodium acetate. The longer chain carbonylic compounds wherein R1 and R2 each represents an alkyl group, n represents a positive integer of from 1 to 6, R represents a member selected from the group consisting of hydrogen, an alkyl group, an aralkyl group, an aryl group and a group of the following general formula: V

NO wHPOHLM V V R1 7 wherein Ri, R2 and n'each represents the values given above, Z represents a member selected from the group consisting of a .hydrazono group an allzylhydrazono group, a dialkylhydrazono roup,

,anfaralkylhydrazono group, a diaralkylhydrazono group, an arylhydrazono group, a diarylhydrazono group, a hydroximino group, a carbamylhydrazono group, a thiocarbamylhydrazono groupand a guanylhydrazono group when n represents a positive integer of froml to 6, and-when nrepresents apositive integer of from 2 to 6, Z represents an oxygen atom in addition'to the groups recitedzabove for Z.

2. A photographic gelatino-silver-halide emul- Sion sensit zed with at least one sensitizing dye selected from the groupconsisting of 2-cyanine salts and. oxacarbocyanine salts andcontaining, as asupersensitizer, at least one compound selected from those which are represented by --the following general formula:

wherein R1 and R2 each represents an alkyl group, n represents a positive integer of from 1 to .6, R represents a memberselected from the group consisting. of hydrogen, an alkyl group, an aralkyl group, an aryl group and a group of the following general formula:

R1 wherein R1, R2 and n each represents the values givenabove, Z represents a member selected from the group consisting of a hydrazono group, an alkylhydrazono group, a dialkylhydrazono group, an aralkylhydrazono group, a diaralkylhydrazono group, an arylhydrazono group, a diarylhydrazono group, a hydroximino group, a carba' ylhydrazono group, a thiocarbamylhydrazono group and a guanylhydrazono group when n represents a positive integer of. from 1 to 6,'andlwhen n represents a positive integer of from 2 to 6,'Z represents an oxygen atom in'addition to .the groups recited above for Z.

3. A photographic gelatino-silver-halide developing-out emulsion sensitized with at least one sensitizing dye selected fromthe group consisting of 2-cyanine salts andoxacarbocyanine salts and containing, as a supersensitizer, atleast one compound selected from those which are represented by the following general formula:

R1 wherein 1R1 and R2 each represents an alkyl group, n represents a positive integer of from 1 to 6, R represents a member selected from the group consistingof hydrogen, an alkyl group, an ar'alkyl group, an aryl group and a group of the following general formula:

R1 whereinR1, R2 and n each represents the values given above, Z represents a member selected from the groupconsisting of a hydrazono group, an alkylhydrazono group, a dialkylhydrazono group, an aralkylhydrazono group, a diaralkylhydrazono group, an arylhydrazono group, a diarylhydrazonogroup, a hydroximino group,v a-carbarnylhydrazono group, a thiocarbamylhydrazono group and a guanylhydrazono group. when n represents a positive integer of from- 1 i706, and when n represents a'positiveintegerof from-'2 to 6, Z represents an oxygen atom in addition to'the groups recited above for Z.

4. A photographic gelatino silver-bromiodide developing-out emulsionsensitized with at least one sensitizing dye selectedfrorn the group consisting of- 2'-cyanine salts and oxacarbocyanine salts and containing, as a supersensitizer, atleast one compound selectedfrom' those Which are repres ntedbythe following general formula:

wherein R1 and R2 each represents an alkyl group, n represents a positive integer of from 1 to 6, R represents a member-selected from thegroup "consisting of hydrogen, an alkyl group, an aralkyl group, 'an aryl group anda group of the followingg'enrali formula:

NL '-(CH =CH)n-1 wherein-R1, Rz and neach-represents the values given-above, Z represents a member selected from thegro p on ti o phydr zon r up, an alkylhyd a ono gr p, a dialkylhydm on up, an aralkylhydrazono group, a diaralkylhydrazono gm ipgan arylhydrazono group,ja diaryl-hydrazono roup, a 'hy ioxim no gr un-a r mylhy razonolgroup, a thiocarbarnylhydrazono group and a-guanylhydrazono group when n represents a positive integer of from 1 to 6, and when n represents a positive integer of from 2 to 6, Z representsan oxygen atom in addition to the groups recited above for Z. a

5. A photographic gelatino-silvenhalide developing-out emulsion sensitized with at least one 2-cyanine sensitizing dye and containing, as a 'superse'ns'itizeni atleast one compound selected rromtnose which are represented'by the following'genr'al formula:

wherein R1 and Rz'each represent an alkyl group, n'represents a positive integer of from 1 to 6, R represents a member selected from the group consisting of hydrogen, an alkyl group, an 'a'r'alkyl' group,"an aryl group'a'nda group of the following general formula:

a supersensitizer, at least one compound selected from-those which are represented by the following general formula:

n represents a positive integer of from 1 to 6, R

represents a, member selected from the group consisting of hydrogen, an alkyl group, an aralkyl group, an aryl group and a group of the following general formula:

wherein R1, R2 and n each represents the values given above, Z represents a member selected from the group consisting of a hydrazono group, an alkylhydrazono group, a dialkylhydrazono group, an aralkylhydrazono group, a diaralkylhydrazono group, an arylhydrazono group, a diarylhydrazono group, a hydroximino group, a carbamylhydrazono group, a thiocarbamylhydrazono group and a guanylhydrazono group when n represents a positive integer of from 1 to 6, and when n represents a positive integer of from 2 to 6, Z represents an oxygen atom in addition to the groups recited above for Z.

7. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with at'least one 1,1-dialkyl-2,2-cyanine salt and containing, as a supersensitizer, at least one compound selected from those which are represented by the following general formula:

wherein R1 and R2 each represents an alkyl group, n represents a positive integer of from 1 to 6, R represents a member selectedfrom the group consisting of hydrogen, an alkyl group, an aralkyl group, an aryl group and a group of the following general formula:

wherein R1, R2 and 11, each represents the values given above, Z represents a member selected from the group consisting of a'hydrazono group, an alkylhydrazono group, a dialkylhydrazono group, an aralkylhydrazono group, a diaralkylhydrazono group, an arylhydrazono group, a diarylhydrazono group, a hydroximino group, a carbamylhydrazono group, a thiocarbamylhydrazono group and a guanylhydrazono group when n represents a positive integer of from 1 to 6, and when n represents a positive integer of from 2 to 6, Z represents an oxygen atom in addition to the groups recited above for Z.

8. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with at least one 1,1-dialkyl-2,2-cyanine salt and containing, as a supersensitizer, at least one of the ketones which are represented by the following general formula:

wherein R1 and R2 each represents an alkyl group group, and anaryl group.

'12 and R represents a member selected from the group consisting of an alkyl group, an aralkyl 9. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with at least one 1,1 -dialkyl-2,2'-cyanine salt in whichthe alkyl groups each contain from -1 to 2 carbon atoms, the emulsion containing as a supersensitizer' at least one of the ketones which are repre sented by the following general formula: V

R2 7 r I R N oH=oH =o R5 a a V wherein R1 and R2 each represents an alkyl group and R represents a member selected from the group consisting of an alky1 group, an aralkyl group, and an aryl group. 7

10. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with at least one 1,1-'dialky1-2,2-cyanine salt in which the alkyl groups each contain from 1 to 2 carbon atoms, the emulsion containing, as a supersensitizer, at leastone of the compounds which are represented by the following general formula:

wherein R1 and R2 each represents an alkyl group, Z represents a member selected from the group consisting of an oxygen atom, a hydrazono group, an alkylhydrazono group, a dialkylhydrazono group, an aralkylhydrazono group, a diaralkylhydrazono group, an arylhydrazono group, a diarylhydrazono group, a hydroximino group, a carbamylhydrazono group, a thiocarbamylhydrazono group and a guanylhydrazono group.

11. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with at least one 1,1-dialkyl-2,2-cyanine salt in which the alkyl groupseach contain from 1 to 2 carbon atoms, the emulsion containing, as a supersensitizer, at least one of the compound which are represented by the following formula:

, one l,1"-dialkyl-2,2-cyanine salt in which the alkyl groups each contain from 1 to 2 carbon atoms, the emulsion containing, as a supersensitizer, p-dimethylaminocinnamalacetophenone.

14. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with at least one 1,l-dialkyl-2,2-cyanine salt in which the alkyl groups each contain from 1 to 2 carbon atoms, the emulsion containing, as a supersensitizer, p-dimethylaminocinnamic aldehyde.

15. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with at least one 1,1'-dialkyl- 2,2-cyanine salt in which the alkyl group contains from 1 to 2 carbon atoms, the emulsioncontaining, as a supersensitiz er, at

least one of the compounds which are represented by the following general formula:

wherein R1 and R2 each represents an alkyl group, and Z represents the carbamylhydrazono group.

16. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with 1,1'-diethyl-2,2'-cyanine iodide, the emulsion containing, as a supersensitizer, p-dimethyl-aminocinnamalacetophenone.

1'7. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with 1,1-diethyl-2,2-cyanine iodide, the emulsion containing, as a supersensitizer, p-dimethyl-aminocinnamic aldehyde.

14 18. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with 1,1'-diethy1-2,2-cyanine iodide, the emulsion containing, as a supersensitizer, p-dimethylaminocin- 5 namic aldehyde semicarbazone.

EDWARD B. KNOTT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 15 2,313,922 Carroll et al. Mar. 16, 1943 2,316,268 Mareis Apr. 13, 1943 

